The present invention relates to fabric care systems that enhance the anti-wrinkle properties of fabric. The systems of the present invention also comprise compositions comprising cationic silicones. The present invention further relates to methods for providing an anti-wrinkle benefit to fabric.
Fabric, especially cellulose based fabric, inter alia, cotton, has a propensity to wrinkle either upon drying after the laundry process or when worn. Permanent press finishes have been used to provide a crisp, smooth garment, however, permanent press processes must modify the fabric itself, either by cross linking of the cellulose fiber or by applying a less flexible coating material. The breathability, especially of cotton, is sacrificed if the applied coating or crosslinking fills the interstices of the fiber cells.
For natural fiber, inter alia, cotton, most coatings must be chemically reacted with the fabric fiber itself in order to obtain the desired level of anti-wrinkle properties. This type of treatment also can occur during the synthesis of polyester fabrics as well. To achieve controlled deposition, there must be an affinity for a fabric surface and the ability of a substrate to lie down onto the garment surface is key to achieving and maintaining a smooth fabric surface.
There is, therefore, a long felt need in the art for a fabric treatment system which provides anti-wrinkle benefits to fabric regardless of fabric type, and which does not require chemical bonding of the substrate to the fabric itself.
The aforementioned needs have been met in that it has been surprisingly discovered that certain cationic silicone compounds when used in combination with materials capable of scavenging compounds having an anionic charge which can affect active deposition onto fabric, together provide anti-wrinkle benefits to fabric. The benefits of the present invention can be delivered by way of a liquid fabric conditioning composition. The cationic silicones of the present invention can be part of a system used to enhance the properties of fabric.
The first aspect of the present invention relates to fabric enhancement compositions comprising:
a) from about 0.0 1% to about 20% by weight, of a cationic silicone polymer or copolymer having the formula:
[CAP]xe2x80x94Zmxe2x80x94[CAP]
xe2x80x83wherein each Z unit independently has the formula:
xe2x80x94(R)xxe2x80x94Wxe2x80x94(R)xxe2x80x94
x is 0 or 1;
W is a siloxane unit having the formula: 
each R1 unit is a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; n is an index from 1 to 500;
R is a nitrogen atom containing backbone unit having the formula:
B is a unit comprising at least one secondary, tertiary, or quaternary amino moiety, or mixtures thereof; R2 is a coupling unit having the formula: 
R3 is C2-C12 linear or branched alkylene; R4 is hydrogen, or a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; y is 0 or 1; z is from 0 to 50;
B is a unit comprising at least one secondary, tertiary, or quaternary amino moiety, or mixtures thereof;
R2 is a coupling unit having the formula: 
R3 is C2-C12 linear or branched alkylene; R4 is hydrogen, or a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; z is from 0 to 50;
L is a linking unit; y is 0 or 1;
b) from about 1% to about 30% by weight, of a scavenger effective in scavenging compounds comprising an anionic unit; and
c) the balance a carrier system.
The present invention further relates to a method for providing fabric enhancement and anti-wrinkle benefits to fabric, said method comprising the step of contacting fabric with a rinse-added composition as described herein.
An additional aspect of the present invention relates to a fabric rinse additive composition comprising the cationic silicone polymer and/or copolymer described above. The present invention further relates a method for providing fabric enhancement and anti-wrinkle benefits to fabric, said method comprising the step of contacting fabric with a fabric rinse additive composition as described herein. The present invention relates further still to the use of a fabric rinse additive composition as described herein in conjunction with a fabric softening composition to provide improved fabric softening and anti-wrinkling benefits.
These and other objects, features, and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to rinse-added fabric enhancement compositions wherein one primary benefit is anti-wrinkling of fabric. This anti-wrinkling benefit is not only present as the, fabric emerges from the laundry cycle. but this benefit is sustained while the fabric is worn and can be renewed upon subsequent treatment at the next laundry cycle. The present invention is especially useful when used to provide an anti-wrinkle benefit to articles of manufacture used as garments, inter alia, trousers, blouses, and the like.
This benefit is surprisingly independent of fabric type. This benefit is effective over a wide rang of fabric types because, unlike permanent press treatments, the compounds which provide the benefits do not react with the fabric fibers themselves. The ingredients which comprise the present invention are surprisingly fabric substantive across a range of fabric types (from hydrophobic to hydrophilic fibers) and are able to modify the properties of said fabric without the loss of other desirable fabric properties.
Definitions
For the purposes of the present invention the term xe2x80x9chydrocarbylxe2x80x9d is defined herein as xe2x80x9cany unit which comprises carbon and hydrogen atoms, whether linear, branched, cyclic, acyclic, and regardless of how many of the hydrogen atoms are substituted for with a suitable xe2x80x9csubstitutedxe2x80x9d unit as defined herein below.xe2x80x9d Non-limiting examples of xe2x80x9chydrocarbylxe2x80x9d units include methyl, benzyl, 6-hydroxyoctanyl, m-chlorophenyl, 2-(N-methylamino)propyl, and the like.
The term xe2x80x9csubstitutedxe2x80x9d is used throughout the specification and for the purposes of the present invention the term xe2x80x9csubstitutedxe2x80x9d is defined as xe2x80x9creplacement of a hydrogen atom, two hydrogen atoms, or three hydrogen atoms from a carbon atom to form a moiety, or the replacement of hydrogen atoms from adjacent carbon atoms to form a moiety.xe2x80x9d For example, a substituted unit that requires a single hydrogen atom replacement includes halogen, hydroxyl, and the like. A two hydrogen atom replacement includes carbonyl, oximino, and the like. Three hydrogen replacement includes cyano, and the like. The term substituted is used throughout the present specification to indicate that a moiety, inter alia, aromatic ring, alkyl chain, can have one or more of the hydrogen atoms replaced by a substituent. For example, 4-hydroxyphenyl is a xe2x80x9csubstituted aromatic carbocyclic ringxe2x80x9d, and 3-guanidinopropyl is a xe2x80x9csubstituted C3 alkyl unit.xe2x80x9d
The following are non-limiting examples of moieties, which can replace hydrogen atoms on carbon to form a xe2x80x9csubstituted hydrocarbylxe2x80x9d unit:
i) xe2x80x94NHCOR30;
ii) xe2x80x94COR30;
iii) xe2x80x94COOR30;
iv) xe2x80x94COCHxe2x95x90CH2;
v) xe2x80x94C(xe2x95x90NH)NH2;
vi) xe2x80x94N(R30)2;
vii) xe2x80x94NHC6H5;
viii) xe2x95x90CHC6H5;
ix) xe2x80x94CON(R30)2;
x) xe2x80x94CONHNH2;
xi) xe2x80x94NHCN;
xii) xe2x80x94OCN;
xiii) xe2x80x94CN;
xiv) F, Cl, Br, I, and mixtures thereof;
xv) xe2x95x90O;
xvi) xe2x80x94OR30;
xvii) xe2x80x94NHCHO;
xviii) xe2x80x94OH;
xix) xe2x80x94NHN(R30)2;
xx) xe2x95x90NR30;
xxi) xe2x95x90NOR30;
xxii) xe2x80x94NHOR30;
xxiii) xe2x80x94CNO;
xxiv) xe2x80x94NCS;
xxv) xe2x95x90C(R30)2;
xxvi) xe2x80x94SO3M;
xxvii) xe2x80x94OSO3M;
xxviii) xe2x80x94SCN;
xxix) xe2x80x94P(O)H2;
xxx) xe2x80x94PO2;
xxxi) xe2x80x94P(O)(OH)2;
xxxii) xe2x80x94SO2NH2;
xxxiii) xe2x80x94SO2R30;
xxxiv) xe2x80x94NO2;
xxxv) xe2x80x94CF3, xe2x80x94CCl3, xe2x80x94CBr3;
xxxvi) and mixtures thereof;
wherein R30 is hydrogen, C1-C20 linear or branched alkyl, C6-C20 aryl, C7-C20 alkylenearyl, and mixtures thereof; M is hydrogen, or a salt forming cation. Suitable salt forming cations include, sodium, lithium, potassium, calcium, magnesium, ammonium, and the like. Non-limiting examples of an alkylenearyl unit include benzyl, 2-phenylethyl, 3-phenylpropyl, 2-phenylpropyl.
Cationic Silicone Polymers and Copolymers
The compositions of the present invention comprise one or more cationic silicone polymers or copolymers. These compounds have the formula:
[CAP]xe2x80x94Zmxe2x80x94[CAP]
wherein each unit Z is a silicone comprising unit. Each Z unit can be the same of different from other Z units present in the molecule, however, one aspect of the present invention relates to embodiments wherein all Z units have a uniform composition. However, in this aspect of the invention, especially when the resulting compounds are polymeric, there will be a variation in the exact structure of the Z units primarily due to the variation in the chain length of the unit. Other aspects of the present invention, as discussed herein below comprise copolymers wherein more than one type or class of Z unit is present.
Z units have the formula:
xe2x80x94(R)xxe2x80x94Wxe2x80x94(R)xxe2x80x94
wherein the index x is 0 or 1; W is a siloxane unit having the formula: 
wherein each R1 unit is a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; n is an index from 1 to 500. In one embodiment of the present invention R1 is a unit selected from the group consisting of:
i) C1-C22 linear or branched alkyl;
ii) C3-C22 cycloalkyl;
iii) C6-C22 aryl;
iv) C7-C22 alkylenearyl;
v) C1-C22 linear or branched fluoroalkyl;
vi) C2-C22 linear or branched alkenyl;
vii) C1-C22 linear or branched alkoxy; and
viii) mixtures thereof.
Another aspect of the present invention provides R1 units which are all identical, for example, each R1 unit is methyl. Siloxane units wherein each R1 unit is methyl has the general formula: 
wherein the index n will vary depending upon the choice of the formulator. In one embodiment of the present invention, a single siloxane unit is used in a Z unit, wherein n is 1.
R is a nitrogen atom containing backbone unit having the formula:
xe2x80x94[(L)yxe2x80x94(R2)yxe2x80x94(L)y]xe2x80x94Bxe2x80x94[(L)yxe2x80x94(R2)yxe2x80x94(L)y]xe2x80x94
wherein B is a backbone unit comprising at least one amino unit, said amino units selected from the group consisting of secondary amino units, tertiary amino units, quaternary amino units, and mixtures thereof having the formula: 
iii) mixtures thereof
wherein each R5 is independently:
i) C2-C12 linear or branched alkylene;
ii) C6-C12 arylene;
iii) C7-C22 alkylenearylene;
iv) an alkyleneoxy unit having the formula:
xe2x80x94(R11O)a(R11O)b(R11O)c(R11)xe2x80x94
xe2x80x83wherein R11 is a C2-C12 alkylene unit, the indices a, b, and c are from 0 to 100;
v) a linking unit derived from a dibasic acid, glycidyl ether, or mixtures thereof having the formula:
xe2x80x94[C(O)]d(R11O)a(R12)e[C(O)]dxe2x80x94
xe2x80x83wherein R12 is C1-C20 linear or branched alkylene; xe2x80x94CH2CHOHCH2xe2x80x94, and
xe2x80x83mixtures thereof, a is from 0 to 100, d is 0 or 1, e is from 0 to 20;
each R6 is independently:
i) hydrogen;
ii) C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety;
iii) two R6 units from the same nitrogen atom can be taken together to form an aromatic or non-aromatic, quaternized or non-quaternized heterocyclic unit;
iv) two R6 units each from adjacent nitrogen atoms can be taken together to form an aromatic or non-aromatic, quaternized or non-quaternized heterocyclic unit;
v) one R6 unit can be taken together with a R unit to form an aromatic or non-aromatic, quaternized or non-quaternized heterocyclic unit;
vi) and mixtures thereof;
A is a water soluble anion; j is from 0 to 6, k is from 0 to 1.
Non-limiting examples of B units include: 
viii) and mixtures thereof.
Other embodiments include amino backbone units which are derived from amino acids, for example, W units, a portion of which includes a moieties having the formula: 
R2 is a coupling unit having the formula: 
R3 is C2-C12 linear or branched alkylene; R4 is hydrogen, or a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety. In one embodiment of the present invention, R3 is n-propylene and R4 are each hydrogen. The index z has the value 0 or 1. The R2 unit can be typically formed by the reaction of an epoxy unit having the general formula: 
and a unit capable of opening the epoxy ring.
One embodiment of the present invention utilizes the R2 unit having the formula: 
L is a linking unit which is capable of providing a link between the amino containing backbone unit B and other units comprising the backbone. Linking units can be any suitable combination of atoms except highly reactive or unstable combinations, non-limiting examples of which include, Oxe2x80x94O bonds, Nxe2x80x94O bonds, and the like.
Non-limiting examples of suitable linking units includes units selected from the group consisting of:
i) xe2x80x94[C(R7)2]pxe2x80x94; wherein p is from 1 to 22;
ii) xe2x80x94[C(R7)2]p(CHxe2x95x90CH)qxe2x80x94; wherein p is from 0 to 12; q is from 1 to 6;
iii) xe2x80x94C(X)xe2x80x94;
iv) xe2x80x94OC(X)xe2x80x94;
v) xe2x80x94C(X)Oxe2x80x94;
vi) xe2x80x94[C(R7)2]qC(X)X(R8O)pxe2x80x94; wherein p is from 0 to 12; q is from 1 to 6;
vii) xe2x80x94(OR8)pXC(X)[C(R7)2]qxe2x80x94; wherein p is from 0 to 12; q is from 1 to 6;
viii) xe2x80x94C(X)NR7xe2x80x94;
ix) xe2x80x94C(X)R8C(X)xe2x80x94;
x) xe2x80x94C(X)NR7C(X)xe2x80x94;
xi) xe2x80x94C(X)NR7R8NR7C(X)xe2x80x94;
xii) xe2x80x94NR7C(X)xe2x80x94;
xiii) xe2x80x94NR7C(X)NR7xe2x80x94;
xiv) xe2x80x94NR7C(X)R8NR7xe2x80x94;
xv) xe2x80x94NR7R8C(X)NR7xe2x80x94;
xvi) xe2x80x94NR7C(X)R8C(X)Oxe2x80x94;
xvii) xe2x80x94OC(X)R8C(X)NR7xe2x80x94;
xviii) xe2x80x94NR7C(X)R8C(X)Oxe2x80x94;
xix) xe2x80x94NR7C(X)NR7R8xe2x80x94;
xx) xe2x80x94R8NR7C(X)NR7xe2x80x94;
xxi) xe2x80x94NR7C(X)NR7R8xe2x80x94;
xxii) xe2x80x94R8NR7C(X)NR7R8xe2x80x94;
xxiii) xe2x80x94NR7xe2x80x94;
xxiv) xe2x80x94R8NR7xe2x80x94;
xxv) xe2x80x94NR7R8xe2x80x94;
xxvi) xe2x80x94NR7Nxe2x95x90Nxe2x80x94;
xxvii) xe2x80x94NR7NR7xe2x80x94
xxviii) xe2x80x94OR8xe2x80x94;
xxix) xe2x80x94R8Oxe2x80x94;
xxx) xe2x80x94(R8)uC(X)(R8)uxe2x80x94;
xxxi) xe2x80x94(R8)uOC(O)(R8)uxe2x80x94;
xxxii) xe2x80x94(R8)uC(O)O(R8)uxe2x80x94;
xxxiii) xe2x80x94(R8)uOC(O)O(R8)uxe2x80x94;
wherein R7 is hydrogen, C1-C22 linear or branched alkyl; C1-C22 cycloalkyl; C1-C22 linear or branched fluoroalkyl; C2-C22 linear or branched alkenyl; C6-C22 aryl; C7-C22 alkylenearyl; and mixtures thereof; R8 is C2-C20 linear or branched, substituted or unsubstituted alkylene; C7-C20 alkylenearylene; C6-C20 substituted or unsubstituted arylene; X is oxygen, sulfur, xe2x95x90NR7, and mixtures thereof; u is 0 or 1.
The index y is 0 or 1.
One aspect of the present invention relates to embodiments wherein an xcex1-halo carboxylic acid ester, typically an xcex1-chloroacetic acid polyoxyethylene ester, is used as a linking unit, said units having the formula:
xe2x80x94[CH2]qC(O)O(CH2CH2O)pxe2x80x94 or xe2x80x94(OCH2CH2)pOC(O)[CH2]qxe2x80x94
wherein p is from 1 to 12, specific embodiments of which include q is equal to 1, while p is equal to 3, 6, and 8 respectively.
[CAP]xe2x80x94unit are units which end, terminate, or truncate the polymer, copolymer, or oligomeric chain. The term xe2x80x9ctruncatexe2x80x9d signifies the fact the formulator may provide a specific end capping unit [CAP] or may allow the chain to terminate from the lack of reactive materials (control of stoichiometry) or by quenching. In addition, it will be recognized by the formulator that the chain elongation steps may be truncated by solvolysis or by reaction with an impurity. For example, the formulator may desire the polymers of the present invention to continue adding units by a reaction having the scheme: 
However, an impurity having a nucleophilic center, may react to truncate the chain prematurely, an non-limiting example of which is depicted by the scheme: 
The formulator may also provide specific capping units. One embodiment of the present invention provides [CAP] units selected from the group consisting of: 
vi) mixtures thereof;
wherein R1 is the same as defined herein above, each R9 is independently C1-C12 linear or branched alkylene, C6-C12 arylene, C7-C22 alkylenearylene; R10 is hydrogen, or a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; two R10 units from the same nitrogen atom, two R10 units each from adjacent nitrogen atoms, or one R10 unit can be taken together with a R5 unit or an R1 unit to form an aromatic or non-aromatic, quaternized or non-quaternized heterocyclic unit, and mixtures thereof; A is a water soluble anion; j is from 0 to 6, k is from 0 to 1.
Another aspect of the present invention provides for W units as capping units, for example, a polymer having the formula: 
a non-limiting example of which is a polymer having the formula: 
A non-limiting example of a capping unit includes: 
The backbones of the present invention may comprise a quaternary ammonium unit and therefore the formulator will provide a counter ion, A. These counter ions can be any suitable water soluble anion. In order to formulate the polymeric materials of the present invention, it may be necessary to protonate, through the use of acids, one or more backbone secondary amino units. The secondary amino units (protonated backbone nitrogens) may have for their counter ions any number of suitable organic acids or combinations thereof. Non-limiting examples include acetic acid, tri-basic citric acid, mono-basic citric acid, 50/50 acetic/lauric acids, and the like.
One aspect of the present invention relates to cationic silicone copolymers having two different nitrogen containing B units, for example the oligomer having the formula: 
The following table illustrates non-limiting examples of embodiments of this aspect of the present invention, where m1=m and m2=1.
For the above examples in Table I, the secondary amino units (protonated backbone nitrogens) have for their counter ions any number of suitable organic acids or combinations thereof. Non-limiting examples include acetic acid, tri-basic citric acid, mono-basic citric acid, 50/50 acetic/lauric acids, and the like.
A further aspect of the present invention relates an embodiment having the formula: 
wherein B is selected from the group consisting of: 
wherein n has an average value of from 35 to 50, in two embodiments, n is 45 and 46 respectively, whereas in other embodiments n has the value of from 100 to 110, in one specific embodiment n is 107, the indices a, b, and c are such that (a+c) is from 0 to 20 and b is from 1 to 200.
Another aspect of the present invention relates to compositions which comprise cationic polymers which are formed by a process comprising the steps of:
A) reacting one equivalent of a diamine having the formula: 
xe2x80x83wherein each R5 is independently C2-C12 linear or branched alkylene, C6-C12 arylene, C7-C22 alkylenearylene, an alkyleneoxy unitxe2x80x94(R11O)a(R11O)b(R11O)c(R11)xe2x80x94, wherein R11 is a C2-C12 alkylene unit, the indices a, b, and c are from 0 to 100; R6 is hydrogen, or a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; two R6 units from the same nitrogen atom, two R6units each from adjacent nitrogen atoms, or one R6 unit can be taken together with a R5 unit to form an aromatic or non-aromatic, quaternized or non-quaternized heterocyclic unit, and mixtures thereof; with one equivalent of an epoxide having the formula: 
xe2x80x83wherein L is a linking unit; W is a siloxane unit having the formula: 
xe2x80x83each R1 unit is a C1-C22 linear or branched, substituted or unsubstituted hydrocarbyl moiety; n is an index from 1 to 500; R3 is C2-C12 linear or branched alkylene; y is 0 or 1; to form a cationic silicone polymer comprising one or more amino units, said polymer comprising units having the formula: 
B) optionally reacting said cationic silicone polymer with one or more equivalents of a quaternizing agent thereby quaternizing one or more of said amino units.
The following are non-limiting examples of processes for making the cationic polymers of the present invention.